CN115707724A - High-stability polyglycolide derivative and preparation method thereof - Google Patents
High-stability polyglycolide derivative and preparation method thereof Download PDFInfo
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Abstract
A high stability polyglycolide derivative and its preparation method are provided. The invention adopts a continuous reaction extrusion mode to prepare the high-stability Polyglycolide (PGA) derivative, which is obtained by blending and reacting components containing the polyglycolide and aliphatic monohydric alcohol. The method comprises the following specific steps: the continuous double-screw extrusion mode is adopted, PGA is prepared through monomer polymerization, and then high-boiling-point aliphatic monohydric alcohol is introduced to react and seal the end carboxyl of the PGA to obtain the PGA derivative. The modified PGA derivative effectively reduces the acid value of PGA and improves the thermal stability of the PGA, and provides an effective scheme for improving the ester bond stability of the PGA.
Description
Technical Field
The invention belongs to the field of degradable materials, and particularly relates to a high-stability polyglycolide derivative and a preparation method thereof.
Background
Degradable materials generally refer to materials that can eventually break down into water and carbon dioxide under conditions of composting, natural light, and the like. Can effectively solve the environmental pollution caused by widely using non-degradable plastic products and realize sustainable development. The commonly used degradable materials mainly include polylactic acid (PLA), polycaprolactone (PCL), polyhydroxyalkanoate (PHA), a copolymer of butylene adipate and butylene terephthalate (PBAT), polyglycolide (PGA) and the like. Among them, PGA is a linear aliphatic polyester having the simplest chemical structure, is a biodegradable polymer material having good biocompatibility and uniqueness, and is widely used in surgical sutures, orthopedic fixation, tissue repair materials, drug controlled release systems, and the like.
However, in the prior art, as disclosed in chinese patent CN111303457A, the PGA material has a short main chain due to its own structure, and ester bonds in the main chain are not protected by hydrophobic groups, so that the PGA material is very easily hydrolyzed, and thus the PGA material is easily hydrolyzed even when stored at room temperature (23 ℃,70% relative humidity). Since polyester hydrolysis is a self-accelerating reaction, the acid content accelerates hydrolysis, while higher carboxyl end groups accelerate hydrolysis of the polyester material, and also reduce its stability during processing and subsequent use.
The traditional preparation method of PGA, such as Chinese patent CN102634001A, usually adopts batch preparation in a polymerization reaction kettle, and requires high pressure and no water, and the reaction conditions are harsh and the reaction efficiency is not high.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-stability polyglycolide derivative, which improves the ester bond stability of Polyglycolide (PGA) and enables the PGA to have wider application value. According to the method, the PGA is prepared by adopting a continuous double-screw extrusion mode through monomer polymerization, and then the high-boiling-point aliphatic monohydric alcohol is introduced to react and end-cap the terminal carboxyl of the PGA to obtain the PGA derivative, so that the service life of the material is prolonged.
One of the purposes of the invention is to provide a high-stability polyglycolide derivative which is aliphatic monohydric alcohol terminated modified polyglycolide.
Preferably, the boiling point of the aliphatic monohydric alcohol is greater than or equal to 140 ℃, preferably 150-280 ℃;
the aliphatic monohydric alcohol is selected from aliphatic monohydric alcohol with 6-18 carbon atoms, preferably at least one of n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonyl alcohol, n-decyl alcohol and lauryl alcohol;
the acid value range of the polyglycolide is 0.001-10 mu mol/mg, preferably 0.01-5 mu mol/mg;
the content of terminal hydroxyl of the polyglycolide derivative is 0.001-2 mu mol/mg.
The second purpose of the invention is to provide a preparation method of the high-stability polyglycolide derivative, which comprises the step of blending and reacting components including polyglycolide and aliphatic monohydric alcohol to obtain the high-stability polyglycolide derivative.
Specifically, the preparation method comprises the following steps:
premixing components including aliphatic monohydric alcohol and a blocked catalyst, blending the obtained mixture and polyglycolide, adding the mixture and the polyglycolide into a double-screw extruder, and mixing, melting, reacting and extruding to obtain the high-stability polyglycolide derivative; or the like, or a combination thereof,
pre-mixing components including aliphatic monohydric alcohol and end-capping catalyst, respectively adding the obtained mixture and polyglycolide into a double-screw extruder, preferably respectively adding the mixture at the second section of the double-screw extruder, and then carrying out melt blending and reactive extrusion to obtain the high-stability polyglycolide derivative.
In the preparation method, the boiling point of the aliphatic monohydric alcohol is more than or equal to 140 ℃, and is preferably 150-280 ℃; the aliphatic monohydric alcohol is selected from aliphatic monohydric alcohol with 6-18 carbon atoms, preferably at least one selected from hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol and lauryl alcohol;
the end capping catalyst is selected from at least one of metal salts or oxides of IVB group and IVA group, preferably at least one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl zirconate, titanium glycol, antimony glycol and dibutyltin dioctoate, more preferably at least one of tetraethyl titanate, tetrabutyl zirconate and dibutyltin dioctoate;
the acid value range of the polyglycolide is 0.001 to 10 mu mol/mg, and preferably 0.01 to 5 mu mol/mg.
In the preparation method, based on 100 parts by weight of polyglycolide, the dosage of the aliphatic monohydric alcohol is 0.1-10 parts, and the dosage of the end-capping catalyst is 0.001-5 parts; preferably, the amount of the aliphatic monohydric alcohol is 0.1-2 parts and the amount of the blocking catalyst is 0.001-1 part based on 100 parts by weight of the polyglycolide.
The preparation process of the invention is realized by a double-screw extruder which is a co-rotating or counter-rotating double screw, and comprises the following steps: a Micro 27 twin-screw extruder manufactured by Leistritz, germany, which has a function of switching between a co-rotation direction and a counter-rotation direction; a Co-rotating twin screw extruder model number PolyLab, euroLab, etc. manufactured by Thermo Fisher Scientific, USA; ZSK Mcc18 co-rotating parallel twin-screw extruders manufactured by Coperion corporation, germany, and the like. Preferably, the melt reaction temperature of the double-screw extruder is 100-350 ℃, preferably 150-300 ℃; the screw rotating speed of the double-screw extruder is 5-1200 rpm, preferably 30-250 rpm.
In the preparation method of the invention, the polyglycolide can be a commercial product of the polyglycolide, and can also be prepared by adopting a common process. For example, the polyglycolide may be prepared by polymerizing glycolic acid and/or its derivatives by a continuous reactive extrusion process. Specifically, the preparation method of the polyglycolide comprises the steps of adding components including glycolic acid and/or derivatives thereof, an alcohol initiator and a polymerization catalyst into a double-screw extruder, and carrying out mixing, melting and polymerization reaction to obtain the polyglycolide.
Specifically, the glycolic acid and/or the derivative thereof is selected from at least one of glycolic acid, glycolide, methyl glycolate and anhydrides thereof, preferably from glycolide;
the alcohol initiator is selected from aliphatic alcohol, preferably at least one of butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, cetyl alcohol and stearyl alcohol, and is preferably selected from decanol;
the polymerization catalyst is selected from metal compounds, preferably at least one selected from stannous octoate, stannous chloride, aluminum isopropoxide, bismuth acetate and tetrabutyl stannate, and more preferably from stannous chloride;
the total weight of the glycolic acid and the derivative thereof is 100 parts by weight, the dosage of the alcohol initiator is 0.005-0.1 part, and the dosage of the polymerization catalyst is 0.01-5 parts; preferably, the alcohol initiator is used in an amount of 0.01 to 0.5 parts and the polymerization catalyst is used in an amount of 0.01 to 0.05 parts, based on 100 parts by weight of the total weight of the glycolic acid and the derivative thereof.
In the preparation method of the polyglycolide, the double-screw extruder is a co-rotating or counter-rotating double screw, the raw materials are added into the double-screw extruder by a one-step method, and the polyglycolide is obtained by mixing, melting, polymerization reaction and extrusion, and then cooling and granulation, wherein the polymerization reaction temperature is 150-300 ℃, and preferably 160-260 ℃; the screw rotating speed of the double-screw extruder is 5-1200 rpm, preferably 10-260 rpm.
The polyglycolide obtained by the above-mentioned preparation method has a structure represented by the following formula (I):
the invention adopts a continuous reaction extrusion mode to prepare Polyglycolide (PGA) by a double-screw extruder, then the Polyglycolide (PGA) and aliphatic high-boiling-point alcohol are continuously subjected to extrusion reaction, and the PGA is terminated through esterification reaction to obtain the modified polyglycolide derivative. In the esterification reaction, a high-efficiency esterification catalyst is selected, and under the action of the catalyst, the high-boiling-point fatty alcohol end-capping reagent and the terminal carboxyl of the PGA are subjected to esterification reaction, so that the number of the terminal carboxyl of the PGA is reduced, the acid value of the material can be effectively reduced, and the stability of the PGA material is improved.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the PGA is terminated by adopting the high-boiling-point fatty alcohol, so that the acid value of the material is effectively reduced, and the stability of the PGA is improved;
2. according to the invention, PGA is directly and continuously prepared in the double-screw extruder by adopting a reactive extrusion method, and is modified by adopting continuous reactive extrusion on the basis, so that the reaction time is greatly reduced to within several minutes, and the reaction efficiency can be effectively improved;
3. the invention provides a continuous and convenient modification method for improving the stability of PGA, the preparation process is simple and feasible, the industrial continuous production is easy to realize, and the method has wide application prospect.
Drawings
FIG. 1 is a DSC temperature drop curve of commercially available PGA-0 and a modified PGA-0 derivative, in which the abscissa is temperature and the ordinate is heat flow rate;
FIG. 2 is a DSC temperature drop curve of PGA-1 prepared in example 1 and a modified PGA-1 derivative, in which the abscissa is temperature and the ordinate is heat flow rate;
FIG. 3 shows the carboxyl end group contents of commercially available PGA-0 and modified PGA derivatives;
FIG. 4 shows the carboxyl end group contents of PGA-1 prepared in the examples and the PGA-1 derivative after modification;
FIG. 5 shows the 5% weight loss temperatures of PGA-0 and the modified PGA-0 derivative, from left to right, in the order PGA-0, 0.2% n-heptanol-terminated PGA-0 derivative, and 0.2% n-hexanol-terminated PGA-0 derivative;
FIG. 6 shows the 5% weight loss temperatures of PGA-1 and the modified PGA-1 derivative, in order from left to right, PGA-1, 0.6% n-heptanol-terminated PGA-1 derivative, and PGA-2 prepared in comparative example 5;
FIG. 7 is a TGA curve of PGA-0 and PGA-0 derivatives after modification, in which the abscissa is temperature and the ordinate is weight percentage, in which the curve a is PGA-0 and the curve b is PGA-0-0.2%.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The test instruments and test conditions used in the examples were as follows:
melt index (MFR) determination method: according to ISO 1133 standard, the melt index is measured by a Lloyd Davenport MFI-10/230 melt index instrument, the cylinder temperature is 150 ℃, the weight load is 2.16kg, the diameter of a die is 2.095mm, the length is 8mm, the preheating time is 4min, samples are automatically cut at set time intervals, 5 times of averaging are taken, and the measurement result is expressed by grams per 10 minutes (g/10 min).
Thermal performance analysis (DSC): the tests were carried out on a Discovery series Differential Scanning Calorimeter (DSC) manufactured by TA Instruments, inc., with the processing software TAInstructions Trios version 3.1.5, equipped with a calibrated Cooling System 90 mechanical refrigeration accessory. The testing atmosphere is 50mL/min of nitrogen, and the amount of the sample required by the test is 5-10 mg. The test procedure was as follows: the temperature is stabilized at 40 ℃, then the temperature is raised to 220 ℃ at 10 ℃/min and kept constant for 1min to remove the thermal history, then the temperature is lowered to-50 ℃ at 10 ℃/min and kept constant for 1min, and then the temperature is raised to 220 ℃ at 10 ℃/min. And recording the temperature reduction process and the second temperature rise process to research the thermal performance of the sample. By DSC measurement, software can be used to directly derive the crystallization temperature ("T") of a sample c "), melting temperature (" T ") m "), glass transition (" T ") g "), enthalpy change (" H "), etc.
Acid value test: the amount of terminal carboxyl groups of PHA before and after modification was measured by titration. 10mg PHA was dissolved in 20g Dimethylsulfoxide (DMSO) solution at a concentration of 5X10 -3 The preparation method comprises the following steps of carrying out the preparation of a methanol solution of NaOH in mol/L, wherein the indicator is a 1% mass fraction ethanol solution of bromothymol blue. The titration end point is determined when the solution changes from orange to greenish black.
Thermogravimetric Testing (TGA): the test was carried out on a Discovery series thermogravimetric analyzer from thermalanylisis, with the processing software being taiinstruments Trios version 3.1.4. Before testing, starting the machine to preheat until the temperature of a balance cavity is about 40 ℃, weighing 5-10 mg of sample in a ceramic crucible during testing, testing in an air atmosphere with the flow rate of 20mL/min, wherein the temperature rise range is 50-600 ℃, the temperature rise rate is 10 ℃/h, and recording the weight loss curve of the sample.
Preparation of polyglycolide [ example 1 ]:
the catalyst used in the present invention is tetraalkyl titanate selected from Shanghai Yuye Co., ltd, polyglycolide (PGA) is Glycolide (GA) and stannous chloride (Sn (Cl) 2 ) Prepared under reactive extrusion, GA is selected from stannous chloride (Sn (Cl) produced by the Han big Dipper in China 2 ) Manufactured by the Shanghai Michelin reagent, inc.
The preparation method comprises the following steps:
100 parts by weight of GA powder, 0.03 part by weight of decanol and 0.03 part by weight of Sn (Cl) 2 And (4) uniformly mixing. The pellets were extruded from a Eurolab 16 co-rotating twin-screw extruder (screw diameter: 16mm, length-to-diameter ratio L/D = 40/1) from Thermo Fisher scientific Co., U.S.A.. The extruder has 11 segments from the feeding port to the neck mold, which are numbered as 1-11, wherein the 1 st segment only plays the role of feeding, the processing temperature of each segment of the 2-11 segments is 160 ℃, 200 ℃, 230 ℃, 240 ℃, 230 ℃, and the screw rotation speed is set at 20rpm. When the engine runs stably, the maximum value of the torque is 20-30%. The extruder was equipped with a circular neck ring having a diameter of 3mm, and the sample strip was air-cooled from the neck ring and cut into cylindrical pellets having a diameter of 3mm by a cutter. PGA particles prepared by reactive extrusion were named PGA-1.
[ example 2 ] preparation of high-stability polyglycolide derivative
The PGA-1 particles obtained in example 1 were subjected to terminal capping modification in a twin-screw extruder, and the terminal-capping agent n-heptanol and the catalyst tetramethyl titanate were obtained from China national medicine Co. PolyLab HAAKE from Thermo Fisher science and technology, USA, was selected TM Rheomex OS PGA was modified with a PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40/1)It is also good.
100 parts of PGA-1 particles, 0.15 part of tetramethyl titanate and 0.6 part of n-heptanol are premixed, plasticized, reacted and extruded to obtain modified polyglycolide derivative particles (named PGA-1-0.6%). The premixed PGA was fed at a rate of 2kg/h. The formulation, processing parameters and melt index are shown in table 1.
The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃, 220 ℃, 230 ℃, 240 ℃, 230 ℃, 220 ℃ and 160 ℃, the screw speed is set at 50rpm. Feeding the PGA mixture to the 1 st section of the double-screw extruder by using a weight-loss feeder, wherein after the operation is stable, the pressure of the double-screw extruder is 25-35 bar, and the torque is about 20-30%. The extruder is provided with two circular outlets with the diameter of 4mm on the neck mold, a sample strip is extruded from the neck mold, and is cut into cylindrical particles with the length of about 5mm by a granulator through a water bath cooling tank, and the cylindrical particles are collected and packaged for later use after being vacuumized for 4 hours in a vacuum drying box at 70 ℃.
[ example 3 ]
Polyglycolide particles (named PGA-0) (acid value of polyglycolide PGA-0: 0.074. Mu. Mol/mg) purchased from Corbion Purac were subjected to reactive extrusion modification. According to the parts by weight, 100 parts of PGA-0, 0.2 part of n-heptanol, 0.05 part of tetramethyl titanate, 100 parts of PGA-0, 1 part of n-heptanol and 0.25 part of tetramethyl titanate are respectively reacted and extruded to be modified to obtain modified polyglycolide derivative particles (named as PGA-0-0.2 percent and PGA-0-1 percent respectively). The premixed PGA was fed at a rate of 3kg/h. Other conditions were controlled in the same manner as in example 2. The formulation, processing parameters and melt index are shown in table 1.
Comparative example 1
Comparative example 1 in which only PGA-0 was fed to the twin-screw extruder, other conditions were controlled to be the same as in example 2. The obtained particles were named PGA-0-0%. Comparative example 1 the processing parameters and melt index are shown in table 1.
Comparative example 2
Comparative example 2 in order to feed only PGA-1 to the twin-screw extruder, other conditions were controlled to be the same as in example 2. The obtained particles were named PGA-1-0%. The processing parameters and melt index of comparative example 2 are shown in table 1.
[ COMPARATIVE EXAMPLE 3 ]
Comparative example 3 PGA (named PGA-2) obtained by reaction extrusion polymerization using lauryl alcohol as an initiator, 0.02 parts of lauryl alcohol as an initiator and 0.03 parts of stannous octoate as a catalyst, based on 100 parts of GA by weight. Other conditions were controlled in the same manner as in example 1.
Thereafter, only PGA-2 was fed to the twin-screw extruder, and the other conditions were controlled to be the same as in example 2. The obtained particles were named PGA-2-0%. The processing parameters and melt index for comparative example 3 are shown in table 1.
[ example 4 ] A method for producing a polycarbonate
Modified polyglycolide derivative particles (named example 4) were obtained by extrusion modification of 100 parts of PGA-0 with 0.2 parts of n-hexanol and 0.05 parts of tetramethyl titanate. Other conditions were controlled in the same manner as in example 3.
[ example 5 ]
The PGA particles prepared in examples 2 to 4 and comparative examples 1 to 3 were subjected to a melt index test, weight 1.05kg, and temperature 230 ℃. The results are shown in Table 1.
TABLE 1 formulation and processing parameters and melt index for PGA capping reactions
As shown in Table 1, as the amount of n-heptanol added increases, the melt index of PGA-0 decreases from 7.7 to 4.7g/10min, the melt index of PGA-1 decreases significantly from 18 to 7.3g/10min, and the decrease in melt index after the end-capping modification shows that the stability of the end-capping modified PGA is significantly improved as compared to the unmodified PGA starting material. The melt index of the n-hexanol-modified PGA derivative prepared in example 4 was slightly decreased compared to PGA-0, and the end-capping effect of n-hexanol was weaker than that of n-heptanol in example 4 in view of the melt index, indicating that a larger molecular weight of n-heptanol contributed to the end-capping reaction of PGA.
[ example 6 ]
Scanning Calorimetry (DSC) tests were performed on the polyglycolide derivatives obtained in examples 2 to 4 and comparative examples 1 to 3 to measure the cooling crystallization temperature (T) c ) Enthalpy of crystallization (. DELTA.H) c ) And melting temperature (T) of the second heating process m ) Enthalpy of fusion (. DELTA.H) m ) See table 2.
TABLE 2 DSC results of examples 2 to 4 and comparative examples 1 to 3
| T c (℃) | △H c (J/g) | T m (℃) | △H m (J/g) | |
| PGA-0-0％ | 190.5 | 83.3 | 222.3 | 80.7 |
| PGA-0-0.2％ | 189.3 | 80.5 | 221.0 | 77.4 |
| PGA-0-1％ | 189.9 | 80.6 | 221.8 | 80.4 |
| PGA-1-0％ | 174.3 | 68.5 | 223.5 | 69.4 |
| PGA-1-0.6％ | 158.4 | 73.3 | 220.4 | 81.6 |
| PGA-2-0％ | 182.7 | 73.8 | 221.2 | 70.9 |
| Example 4 | 194.5 | 75.1 | 222.6 | 73.2 |
As shown in Table 2, the crystallization temperature of PGA-1-0% prepared by reaction extrusion was lower and the crystallization enthalpy of PGA-1-0% was Δ H as compared with that of the purchased PGA-0-0% c Is also far lower than PGA-0-0%This suggests that PGA-1 prepared by twin-screw is more difficult to crystallize and is less crystalline than PGA-0. In the case of PGA-0, the temperature of the crystallization peak and melting peak is slightly lowered and the enthalpy change of crystallization is also lowered after the addition of the capping agent n-heptanol (PGA-0 to 0.2%, PGA-0 to 1%). Comparing the n-hexanol terminated modified PGA-0 of example 4 with PGA-0-0%, the crystallization enthalpy of the modified PGA-0 is reduced, which indicates that the crystallization performance of the PGA is reduced after being terminated by n-hexanol.
For PGA-1 prepared by twin-screw extrusion, the end capping enables the crystallization/melting temperature to move towards a low temperature direction, and meanwhile, the crystallization/melting enthalpy is remarkably increased, which means that the introduction of the end capping agent enables the crystallization form of the PGA-1 to be changed, so that the end-capped PGA-1 has a more ordered thermodynamic structure, and the thermal stability of the end-capped PGA-1 is favorably improved. It can also be seen in FIG. 2 that the temperature rise curve of PGA-1 after the addition of the end-capping reagent shows a recrystallization peak, indicating that the chain forms an ordered structure at elevated temperatures and the degree of crystallinity increases.
[ example 7 ]
The products prepared in examples 2 to 4 and comparative examples 1 to 3 were dissolved in DMSO at a concentration of 0.05wt% and used at 5X10 -3 And titrating a mol/L NaOH/benzyl alcohol solution, and measuring the content of the terminal carboxyl. The results of obtaining the amount of terminal carboxyl groups (. Mu.mol) per unit mass of PGA are shown in FIGS. 3 and 4. Specific values are shown in Table 3.
TABLE 3 carboxyl end group content of the products obtained in examples 2 to 4 and comparative examples 1 to 3
| Product carboxyl end group content (. Mu. Mol/mg) | |
| PGA-0-0％ | 0.074 |
| PGA-0-0.2％ | 0.020 |
| PGA-0-1％ | 0.022 |
| PGA-1-0％ | 0.087 |
| PGA-1-0.6％ | 0.018 |
| PGA-2-0％ | 0.078 |
| Example 4 | 0.035 |
As can be seen in fig. 3 and 4, the carboxyl end group contents of both the modified PGA-0 and the modified PGA-1 were significantly reduced as the amount of n-heptanol was gradually increased. In FIG. 3, the terminal carboxyl groups of PGA-0 were significantly decreased from 0.074. Mu. Mol/mg of PGA-0 to 0% to 0.02. Mu. Mol/mg (decrease by 73%) after the addition of 0.2% n-heptanol, indicating that a large amount of terminal carboxyl groups had been consumed by the capping agent at this time, and as the terminal carboxyl groups further increased, the terminal carboxyl group content did not further decrease and slightly increased to 0.022. Mu. Mol/mg after the addition of 1% n-heptanol, indicating that the capping effect had been saturated at the higher capping agent content. Similarly, in example 4 in which a certain amount of n-hexanol was added, the acid value was also reduced to 0.035. Mu. Mol/mg. In FIG. 4, the acid value of PGA-1 was decreased from 0.087. Mu. Mol/mg to 0.018. Mu. Mol/mg after the addition of 0.6% of n-heptanol as an end-capping agent. The above acid value results demonstrate that the reactive extrusion capping process of the present invention is effective in reducing the acid value of PHA.
[ example 8 ]
Prepared from examples 2-4 and comparative examples 1-3The modified PGA derivative of (1), subjected to a thermogravimetric test. The 5% decomposition temperatures obtained by the test are shown in FIGS. 5 and 6, and the results of the TG test are shown in FIG. 7. As can be seen in FIGS. 5 and 6, the addition of the capping agent resulted in the T-state of either the commercially available PGA-0 or the PGA-1 produced by twin-screw granulation d,5％ All were increased, indicating that the introduction of the end-capping agent is effective in improving the thermal stability of PGA and reducing thermal decomposition. For PGA-0, 0.2% of PGA-0-0.2 of T was added d,5％ The temperature is remarkably improved from 290 ℃ to 320 ℃. In addition, in example 4, the 5% thermal decomposition temperature of PGA-0 terminated with n-hexanol increased from 289 ℃ to 297 ℃. In FIG. 6, the thermal decomposition temperature of PGA-2 prepared using lauryl alcohol as the initiator was not significantly increased relative to PGA-1 prepared using stannous chloride as the catalyst, indicating that no capping effect was obtained using an aliphatic monohydric alcohol as the initiator. As can be seen in FIG. 7, the overall TAG curve for PGA-0-0.2% is "right-shifted" to higher temperatures, indicating that the thermal stability of PGA is greatly enhanced with the addition of 0.2% capping agent relative to PGA-0.
From the above test results, it can be seen that neither commercially available PGA-0 prepared by a batch process nor PGA-1 obtained by the twin-screw continuous reactive extrusion process of the present invention has superior thermal stability, and that the present invention prepares PGA material by twin-screw continuous reactive extrusion and modifies PGA, thereby effectively reducing the acid value of PGA and improving the thermal stability thereof, providing an effective solution for improving the stability during the thermoplastic processing of PGA, and easily realizing industrial continuous production.
Claims (12)
1. A high-stability polyglycolide derivative is characterized in that the polyglycolide derivative is modified polyglycolide terminated by aliphatic monohydric alcohol.
2. The polyglycolide derivative according to claim 1, which is characterized in that,
the boiling point of the aliphatic monohydric alcohol is more than or equal to 140 ℃, and is preferably 150-280 ℃; and/or the presence of a gas in the atmosphere,
the aliphatic monohydric alcohol is selected from aliphatic monohydric alcohol with 6-18 carbon atoms, preferably at least one selected from hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol and lauryl alcohol; and/or the presence of a gas in the gas,
the acid value range of the polyglycolide is 0.001-10 mu mol/mg, and preferably 0.01-5 mu mol/mg; and/or the presence of a gas in the gas,
the content of terminal carboxyl of the polyglycolide derivative is 0.001-2 mu mol/mg.
3. A process for preparing a highly stable polyglycolide derivative according to claim 1 or 2, which comprises blending components including polyglycolide and aliphatic monohydric alcohol for reaction to obtain said highly stable polyglycolide derivative.
4. The preparation method according to claim 3, wherein the preparation method specifically comprises:
premixing components including aliphatic monohydric alcohol and a blocked catalyst, blending the obtained mixture and polyglycolide, adding the blended mixture and polyglycolide into a double-screw extruder, and performing melt blending and reactive extrusion to obtain the high-stability polyglycolide derivative; or the like, or a combination thereof,
the components including the aliphatic monohydric alcohol and the end-capping catalyst are pre-mixed, the obtained mixture and the polyglycolide are respectively added into a double-screw extruder, and the high-stability polyglycolide derivative is obtained after melt blending, reaction and extrusion.
5. The method according to claim 4,
the boiling point of the aliphatic monohydric alcohol is more than or equal to 140 ℃, and is preferably 150-280 ℃; and/or the presence of a gas in the gas,
the aliphatic monohydric alcohol is selected from aliphatic monohydric alcohol with 6-18 carbon atoms, preferably at least one selected from hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol and lauryl alcohol; and/or the presence of a gas in the gas,
the end capping catalyst is selected from at least one of metal salts or oxides of IVB group and IVA group, preferably at least one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl zirconate, titanium glycol, antimony glycol and dibutyltin dioctoate, more preferably at least one of tetraethyl titanate, tetrabutyl zirconate and dibutyltin dioctoate; and/or the presence of a gas in the atmosphere,
the acid value range of the polyglycolide is 0.001 to 10 mu mol/mg, and preferably 0.01 to 5 mu mol/mg.
6. The method according to claim 4, wherein the aliphatic monohydric alcohol is used in an amount of 0.1 to 10 parts and the capping catalyst is used in an amount of 0.001 to 5 parts, based on 100 parts by weight of the polyglycolide; preferably, the amount of the aliphatic monohydric alcohol is 0.1-2 parts and the amount of the blocking catalyst is 0.001-1 part based on 100 parts by weight of the polyglycolide.
7. The method according to claim 4,
the melting reaction temperature is 100-350 ℃, and preferably 150-300 ℃; and/or the presence of a gas in the gas,
the screw rotating speed of the double-screw extruder is 5-1200 rpm, preferably 30-250 rpm.
8. A process according to claim 4, wherein said polyglycolide is polymerized from glycolic acid and/or derivatives thereof.
9. A preparation method according to claim 8, wherein said polyglycolide is prepared by adding components comprising glycolic acid and/or its derivatives, alcohol initiator, and polymerization catalyst into a twin-screw extruder, and melt blending and polymerization reacting.
10. The production method according to claim 9,
the glycolic acid and/or the derivative thereof is selected from at least one of glycolic acid, glycolide, methyl glycolate and anhydride thereof, preferably from glycolide; and/or the presence of a gas in the gas,
the alcohol initiator is selected from aliphatic alcohol, preferably at least one of butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, cetyl alcohol and stearyl alcohol, preferably decanol; and/or the presence of a gas in the gas,
the polymerization catalyst is selected from metal compounds, preferably at least one selected from stannous octoate, stannous chloride, aluminum isopropoxide, bismuth acetate and tetrabutyl stannate, and more preferably from stannous chloride.
11. The method of claim 9, wherein the alcohol initiator is used in an amount of 0.005 to 0.1 part, and the polymerization catalyst is used in an amount of 0.01 to 5 parts, based on 100 parts by weight of the glycolic acid and the derivative thereof; preferably, the alcohol initiator is used in an amount of 0.01 to 0.5 parts and the polymerization catalyst is used in an amount of 0.01 to 0.05 parts, based on 100 parts by weight of the total weight of the glycolic acid and the derivative thereof.
12. The method of claim 9,
the polymerization reaction temperature is 150-300 ℃, preferably 160-260 ℃; and/or the presence of a gas in the atmosphere,
the screw rotating speed of the double-screw extruder is 5-1200 rpm, preferably 10-260 rpm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104177788A (en) * | 2013-05-28 | 2014-12-03 | 中国科学院理化技术研究所 | Hydrolysis resistant aliphatic polyester resin composition and preparation method thereof |
| CN110041510A (en) * | 2019-03-28 | 2019-07-23 | 杭州华惟生物医药有限公司 | Polyglycolide polymers ultrasonic synthetic method |
| CN111087581A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Method for preparing polyglycolic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177788A (en) * | 2013-05-28 | 2014-12-03 | 中国科学院理化技术研究所 | Hydrolysis resistant aliphatic polyester resin composition and preparation method thereof |
| CN111087581A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Method for preparing polyglycolic acid |
| CN110041510A (en) * | 2019-03-28 | 2019-07-23 | 杭州华惟生物医药有限公司 | Polyglycolide polymers ultrasonic synthetic method |
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